CN102931336B - A kind of GeTe base composite thermoelectric material and preparation method thereof - Google Patents
A kind of GeTe base composite thermoelectric material and preparation method thereof Download PDFInfo
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- CN102931336B CN102931336B CN201210400957.6A CN201210400957A CN102931336B CN 102931336 B CN102931336 B CN 102931336B CN 201210400957 A CN201210400957 A CN 201210400957A CN 102931336 B CN102931336 B CN 102931336B
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Abstract
The present invention provides a kind of composite thermoelectric material, and the chemical formula of described composite thermoelectric material is (GeTe)1‑x(Ag8GeTe6)x, wherein the span of x is 0.02 x 0.20.The present invention also provides for the preparation method of a kind of described composite thermoelectric material.The composite thermoelectric material that the present invention provides is unleaded, has relatively low thermal conductivity and has higher dimensionless figure of merit ZT, having good thermoelectricity capability.
Description
Technical field
The present invention relates to novel energy field of material technology, especially relate to a kind of unleaded middle temperature composite thermoelectric material
And preparation method thereof.
Background technology
Thermoelectric material is a kind of specific function material, utilize its have electric current by time produce thermograde and
The pyroelectric effect producing electromotive force or electric current when two ends exist the temperature difference can realize temperature control, thermo-electric generation and energising system
Cold.It is little, lightweight, without any mechanical rotation part, in work that these refrigeration and electricity generation system have volume
Noiselessness, does not cause environmental pollution, and service life is long, it is easy to the advantages such as control are it is considered to be in the future the most very
Competitive energy substitution material, has wide in terms of following environmental protection energy project and Refrigeration Engineering
Application prospect.
The conversion efficiency of thermoelectric device is to be determined by the performance of thermoelectric material, and the performance of thermoelectric material is then
By dimensionless figure of merit ZT=S2σ T/k weighs, and wherein S is Seebeck (Seebeck) coefficient, σ and
K is electrical conductivity and the thermal conductivity of material respectively, and T is absolute temperature.The thermoelectric material of a kind of excellent performance is necessary
There is high Seebeck coefficient, high conductivity and lower thermal conductivity.
Group IV-VI semi-conductor thermoelectric material, is middle temperature semi-conductor thermoelectric material including PbTe, GeTe and PbSe,
Can be used for the temperature difference electricity generation device that warm area (400-800K) works, especially apply at the recovery of industrial waste heat and automobile
The fields such as engine exhaust heat utilization.Compared with PbTe base thermoelectricity material, GeTe thermoelectric material does not contains Pb, although
The electrical conductivity of GeTe is higher, but its thermal conductivity is the highest, causes its thermoelectric figure of merit ZT less.
Therefore, it is necessary to provide a kind of composite thermoelectric material and preparation method thereof, the most leaded, have relatively low
Thermal conductivity such that it is able to there is high dimensionless figure of merit.
Summary of the invention
The present invention provides a kind of composite thermoelectric material and preparation method thereof.
A kind of composite thermoelectric material, the chemical formula of described composite thermoelectric material is (GeTe)1-x(Ag8GeTe6)x, its
The span of middle x is 0.02 x 0.20.
Wherein, Ag8GeTe6Being distributed in GeTe, x decides the Ag being distributed in GeTe8GeTe6Phase content
And the thermoelectricity capability of material.
The preparation method of a kind of described composite thermoelectric material, including step: according to (GeTe)1-x(Ag8GeTe6)x
The numerical value of middle x, with metal Ge, Te and Ag simple substance as raw material, weighs raw material according to proportioning；The raw material that will weigh
Make and form GeTe base alloy；Described GeTe base alloying pellet is clayed into power, and by described GeTe base
The powder that alloying pellet is worn into carries out discharge plasma sintering, obtains described composite thermoelectric material.
The composite thermoelectric material that the present invention provides, utilizes GeTe-Ag8GeTe6The eutectic transformation of phasor, at GeTe
Matrix introduces the Ag of Dispersed precipitate8GeTe6Second phase, forms the composite thermoelectric material with eutectic structure,
Greatly reduce the thermal conductivity of material, thus improve its thermoelectricity capability.
Accompanying drawing explanation
Fig. 1 is (GeTe)1-x(Ag8GeTe6)xThe X of (x=0.02,0.05 and 0.11) composite thermoelectric material penetrates
Ray diffraction diagram.
Fig. 2 is (GeTe)1-x(Ag8GeTe6)x(x=0.11) microstructure picture of composite thermoelectric material.
Fig. 3 is (GeTe)1-x(Ag8GeTe6)x(x=0,0.02,0.05,0.08 and 0.11) is combined thermoelectricity material
The resistivity of material and the variation relation schematic diagram of temperature.
Fig. 4 (GeTe)1-x(Ag8GeTe6)x(x=0,0.02,0.05,0.08 and 0.11) composite thermoelectric material
The variation relation schematic diagram of Seebeck coefficient and temperature.
Fig. 5 (GeTe)1-x(Ag8GeTe6)x(x=0,0.02,0.05,0.08 and 0.11) composite thermoelectric material
The variation relation schematic diagram of thermal conductivity and temperature.
Fig. 6 (GeTe)1-x(Ag8GeTe6)x(x=0,0.02,0.05,0.08 and 0.11) composite thermoelectric material
The variation relation schematic diagram of dimensionless figure of merit (ZT) and temperature.
Specific implementation method
Below in conjunction with the accompanying drawings a kind of composite thermoelectric material that the technical program provides and preparation method thereof is carried out in detail
Describe in detail bright.
A kind of composite thermoelectric material, the chemical formula of described composite thermoelectric material is (GeTe)1-x(Ag8GeTe6)x, its
The span of middle x is 0.02 x 0.20, preferably 0.02 x 0.15.
Wherein, Ag8GeTe6 the second phase is distributed in GeTe matrix, and x decides and is distributed in GeTe
Ag8GeTe6Phase content and the thermoelectricity capability of material.
A kind of preparation method of described composite thermoelectric material, including step:
The first step, according to (GeTe)1-x(Ag8GeTe6)xThe numerical value of middle x, is former with metal Ge, Te and Ag simple substance
Material, weighs raw material according to proportioning；
Second step, makes the raw material weighed and forms GeTe base alloy；
3rd step；Described GeTe base alloying pellet is clayed into power；
4th step, carries out discharge plasma sintering by the powder that described GeTe base alloying pellet is worn into, and obtains described
Composite thermoelectric material.
Wherein, in the first step, the proportioning of different metal Ge, Te and Ag can be obtained according to the difference of x numerical value.
The span of X is 0.02 x 0.20.
In second step, described raw material is reacted 20 hours in quartz ampoule under 900 degrees celsius, from
And obtain GeTe base alloy.
In the third step, can use planetary ball mill that GeTe base alloy is carried out ball milling.
In the 4th step, carrying out plasma discharging (SPS) sintering under vacuum conditions, vacuum is 1 × 10-2Pa
Time, pressure 30 ~ 50MPa, 600 ~ 650 ° of C of sintering temperature, temperature retention time 5 ~ 10 minutes, institute can be obtained
State composite thermoelectric material.
The composite thermoelectric material (GeTe) prepared1-x(Ag8GeTe6)xX-ray diffractogram as shown in Figure 1 is used to enter
Row characterizes.Fig. 1 illustrates the X-ray diffractogram of composite thermoelectric material when x is 0.02,0.05 and 0.11, and Fig. 2 is
The microstructure picture of described composite thermoelectric material (x=0.11), Fig. 1 and Fig. 2 shows the heat that the present invention prepares
Electric material contains GeTe matrix phase and Ag8GeTe6Second phase.
Refer to Fig. 3, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xResistivity along with temperature rising and
Increase.At the same temperature, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xResistivity high temperature under be less than
The conductivity of GeTe.Refer to Fig. 4, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xSeebeck coefficient with
The rising of temperature and increase, at the same temperature, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xSai Bei
Gram coefficient is slightly less than the Seebeck coefficient of GeTe.Refer to Fig. 5, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)x
Thermal conductivity reduce along with the rising of temperature.Further, at the same temperature, composite thermoelectric material
(GeTe)1-x(Ag8GeTe6)xThermal conductivity the most significantly less than the thermal conductivity of GeTe.Further, at identical temperature,
Along with the increase of x numerical value, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xThermal conductivity numerical value reduce.By Fig. 5
Can draw, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xCompared to GeTe, thermoelectric material can be reduced
Thermal conductivity.Refer to Fig. 6, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xDimensionless figure of merit along with
The rising of temperature and increase.Further, at the same temperature, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)x
Dimensionless figure of merit be all higher than the dimensionless figure of merit of GeTe.Further, at identical temperature, along with x number
The increase of value, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xDimensionless figure of merit numerical value increase.By scheming
6 can draw, composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xCompared to GeTe, thermoelectric material can be increased
Dimensionless figure of merit, thus increase the thermoelectricity capability of material.
Below, specifically illustrate that this technology puts composite thermoelectric material and the preparation thereof that case provides by embodiment 1 to 3
Method.
Embodiment 1
With Ge, Te and Ag as raw material, according to chemical molecular formula (GeTe)0.89(Ag8GeTe6)0.11Weigh
Proportioning also loads in quartz ampoule, and after evacuation, the good quartz ampoule of soldering and sealing is placed in Muffle furnace reacting, reaction
Temperature is 900 ° of C, and the response time is 20 hours, obtains GeTe base alloy；Reaction is obtained GeTe base
Alloy grind into powder, puts in ball grinder together with abrading-ball, is filled with Ar gas after forvacuum, uses planet
Ball mill prepares attritive powder, drum's speed of rotation 200 revs/min, ratio of grinding media to material 20:1, ball under Ar gas shielded
Consume time 8 hours；Powder after ball milling is carried out under vacuum conditions plasma discharging (SPS) sintering, vacuum
Degree is 1 × 10-2Pa, pressure 50MPa, 620 ° of C of sintering temperature, temperature retention time 5 minutes, i.e. obtain
Ag8GeTe6The unleaded composite thermoelectric material (GeTe) being distributed in matrix GeTe matrix0.89(Ag8GeTe6)0.11。
The composite thermoelectric material (GeTe) that the present embodiment prepares0.89(Ag8GeTe6)0.11Thing phase, microstructure and heat
As shown in figures 1 to 6, its thermal conductivity is 1.23W/m.K at 673K to electrical property, is pure GeTe synthermal lower 3.23
The 38% of W/m.K；And its maximum figure of merit (ZT) is 1.15, exceed 125% than the 0.51 of pure GeTe.
Embodiment 2
With Ge, Te and Ag as raw material, according to chemical molecular formula (GeTe)0.95(Ag8GeTe6)0.05Weigh
Proportioning also loads in quartz ampoule, and after evacuation, the good quartz ampoule of soldering and sealing is placed in Muffle furnace reacting, reaction
Temperature is 900 ° of C, and the response time is 20 hours, obtains GeTe base alloy；Reaction is obtained GeTe base
Alloy grind into powder, puts in ball grinder together with abrading-ball, is filled with Ar gas after forvacuum, uses planet
Ball mill prepares attritive powder, drum's speed of rotation 200 revs/min, ratio of grinding media to material 20:1, ball under Ar gas shielded
Consume time 8 hours；Powder after ball milling is carried out under vacuum conditions plasma discharging (SPS) sintering, vacuum
Degree is 1 × 10-2Pa, pressure 50MPa, 620 ° of C of sintering temperature, temperature retention time 5 minutes, i.e. obtain
Ag8GeTe6The unleaded composite thermoelectric material (GeTe) being distributed in matrix GeTe matrix0.95(Ag8GeTe6)0.05。
The composite thermoelectric material (GeTe) that the present embodiment prepares0.95(Ag8GeTe6)0.05Thing phase and thermoelectricity capability such as
Shown in Fig. 1,3-6, its thermal conductivity is 1.98W/m.K at 673K, is the synthermal lower 3.23W/m.K of pure GeTe
61%；And its maximum figure of merit (ZT) is 1.03, exceed 102% than the 0.51 of pure GeTe.
Embodiment 3
With Ge, Te and Ag as raw material, according to chemical molecular formula (GeTe)0.92(Ag8GeTe6)0.08Carry out weighing to join
Comparing and load in quartz ampoule, after evacuation, the good quartz ampoule of soldering and sealing is placed in Muffle furnace reacting, reaction temperature
Degree is 900 ° of C, and the response time is 20 hours, obtains GeTe base alloy；Reaction obtains GeTe base alloy grind
Clay into power, put in ball grinder together with abrading-ball, after forvacuum, be filled with Ar gas, use planetary ball mill
Attritive powder, drum's speed of rotation 200 revs/min, ratio of grinding media to material 20:1, Ball-milling Time 8 is prepared under Ar gas shielded
Hour；Powder after ball milling carries out plasma discharging (SPS) sintering under vacuum conditions, and vacuum is
1×10-2Pa, pressure 50MPa, 620 ° of C of sintering temperature, temperature retention time 5 minutes, i.e. obtain Ag8GeTe6
The unleaded composite thermoelectric material (GeTe) being distributed in matrix GeTe matrix0.92(Ag8GeTe6)0.08。
The composite thermoelectric material (GeTe) that this example prepares0.92(Ag8GeTe6)0.08Thing phase and thermoelectricity capability such as Fig. 1,
Shown in 3-6, its thermal conductivity is 1.62W/m.K at 673K, is the 50% of the synthermal lower 3.23W/m.K of pure GeTe；
And its maximum figure of merit (ZT) is 0.87, exceed 71% than the 0.51 of pure GeTe.
The composite thermoelectric material that the present invention provides, utilizes (GeTe)1-x(Ag8GeTe6)xEutectic transformation, at GeTe
Matrix introduces the Ag of Dispersed precipitate8GeTe6Second phase, forms the composite thermoelectric material with eutectic structure,
Greatly reduce the thermal conductivity of material, thus improve its thermoelectricity capability.
Claims (3)
1. a composite thermoelectric material, described composite thermoelectric material include GeTe matrix phase and Dispersed precipitate in described GeTe matrix mutually in Ag8GeTe6Second phase, wherein, described Ag8GeTe6How much content of the second phase determines the thermoelectricity capability of described composite thermoelectric material；The chemical formula of described composite thermoelectric material is (GeTe)1-x(Ag8GeTe6)x, wherein the span of x is 0.02 x 0.15；GeTe matrix phase and Ag described in described composite thermoelectric material8GeTe6Second phase forms eutectic structure.
2. a preparation method for the composite thermoelectric material described in claim 1, including step:
According to (GeTe)1-x(Ag8GeTe6)xThe numerical value of middle x, with metal Ge, Te and Ag simple substance as raw material, weighs raw material according to proportioning；
The raw material weighed is made and forms GeTe base alloy；
Described GeTe base alloying pellet is clayed into power；And
The powder that described GeTe base alloying pellet is worn into is carried out discharge plasma sintering, obtains described composite thermoelectric material (GeTe)1-x(Ag8GeTe6)x；The raw material weighed is made and forms the method for GeTe base alloy and be: by described weigh raw material loads in quartz ampoule, after evacuation, the good quartz ampoule of soldering and sealing is placed in Muffle furnace reacting, and reaction temperature is 900 DEG C, and the response time is 20 hours, obtains GeTe base alloy；
The powder that described GeTe base alloying pellet is worn into is carried out discharge plasma sintering, obtains described composite thermoelectric material (GeTe)1-x(Ag8GeTe6)xMethod be: powder after ball milling is carried out under vacuum conditions plasma discharging (SPS) sintering, vacuum is 1 × 10-2Pa, pressure 30～50MPa, sintering temperature 600～650 DEG C, temperature retention time 5～10 minutes, i.e. obtain Ag8GeTe6It is distributed in the unleaded composite thermoelectric material in matrix GeTe matrix.
3. the preparation method of composite thermoelectric material as claimed in claim 2; it is characterized in that; by the method that described GeTe base alloying pellet is clayed into power it is: reaction is obtained GeTe base alloy grind into powder; put into together with abrading-ball in ball grinder; it is filled with Ar gas after forvacuum, uses planetary ball mill to prepare attritive powder, drum's speed of rotation 200～400 revs/min under Ar gas shielded; ratio of grinding media to material 20:1, Ball-milling Time 0.5～14 hours.
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| CN103552998B (en) * | 2013-10-17 | 2015-02-04 | 厦门大学 | Preparation method of GeTe microcrystal |
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| CN108735888A (en) * | 2018-04-27 | 2018-11-02 | 同济大学 | Novel Ge antimony tellurium compound thermoelectric material with high concentration vacancy and preparation method thereof |
| CN109950389A (en) * | 2019-03-18 | 2019-06-28 | 清华大学 | Middle warm area high performance thermoelectric material preparation method and middle warm area high performance thermoelectric material |
| CN110491988A (en) * | 2019-07-31 | 2019-11-22 | 深圳大学 | A kind of GeSe base thermoelectricity material and its preparation method and application of Ag doping |
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